Substituted 4-hetaryl-pyrazolines as pest control agents

ABSTRACT

The present invention relates to novel substituted pyrazolines of the formula (I)  
                 
         in which R 1 , R 2 , R 3  and R 4  are as defined in the disclosure, to a plurality of processes for preparing these substances and their use for controlling pests, and to novel intermediates and processes for their preparation.

The present invention relates to novel substituted 4-hetarylpyrazolines,to processes for their preparation and to their use as pesticides.

It is known that certain substituted pyrazolines have insecticidal andacaricidal properties (cf., for example, DE-A 44 16 112, EP-A 0 679 644or EP-A 0 438 690). However, the activity of these compounds is, inparticular at low active compound concentrations and application rates,not always entirely satisfactory.

This invention provides novel substituted 4-hetarylpyrazolines of theformula (I)

in which

-   R¹ represents in each case optionally substituted oxadiazolyl,    thiadiazolyl or tetrazolyl,-   R² represents halogen, haloalkyl, alkoxy, haloalkoxy, alkylthio,    haloalkylthio, alkylsulphonyl, haloalkylsulphinyl,    haloalkylsulphonyl or cyano,-   R³ represents halogen, haloalkyl, alkoxy, haloalkoxy, alkylthio,    haloalkylthio, haloalkylsulphinyl, haloalkylsulphonyl or cyano and-   R⁴ represents hydrogen, cyanomethyl or alkoxycarbonyl.

Depending on the nature and number of substituents, the compounds of theformula (I) may be present as geometrical and/or optical isomers,regioisomers and/or configurational isomers, or as mixtures of theseisomers of varying composition. What is claimed by the invention areboth the pure isomers and the isomer mixtures. Furthermore, it has beenfound that the substituted 4-hetarylpyrazolines of the formula (I) areobtained when

-   a) pyrazolines of the formula (II)    -   in which    -   R¹ and R² are as defined above    -   are reacted with isocyanates of the formula (III)    -   in which    -   R³ is as defined above,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of a catalyst; and-   b) the pyrazoline derivatives of the formula (Ia) according to the    invention obtained in this manner    -   in which    -   R¹, R² and R³ are as defined above    -   are, if appropriate, reacted with halides of the formula (IV)        Hal¹-R⁴  (IV)    -   in which    -   R⁴ is as defined above and    -   Hal¹ represents halogen,    -   if appropriate in the presence of a diluent and if appropriate        in the presence of a base; or-   c) anilines of the formula (V)    -   in which    -   R³ and R⁴ are as defined above    -   are initially reacted with phosgene in the presence of a diluent        and, if appropriate, in the presence of a base, and the        resulting carbamoyl chlorides of the formula (VI)    -   in which    -   R³ and R⁴ are as defined above    -   are, directly or after intermediate isolation, reacted with        pyrazolines of the formula (II)    -   in which    -   R¹ and R² are as defined above    -   in the presence of a diluent and, if appropriate, in the        presence of a base.

Finally, it has been found that the novel substituted4-hetarylpyrazolines of the formula (I) have highly pronouncedbiological properties and are suitable in particular for controllinganimal pests, in particular insects, arachnids and nematodes encounteredin agriculture, in forests, in the protection of stored products and theprotection of materials and in the hygiene sector.

The formula (I) provides a general definition of the4-hetarylpyrazolines according to the invention.

Preferred substituents or ranges of the radicals listed in the formulaementioned above and below are illustrated below:

-   R¹ preferably represents in each case optionally substituted    oxadiazolyl or thiadiazolyl, exemplary substituents being:    optionally substituted alkyl, optionally substituted alkoxy,    optionally substituted alkylthio, optionally substituted aryl or    optionally substituted arylalkyl;    -   and also represents optionally substituted tetrazolyl, exemplary        substituents being: optionally substituted alkyl, in each case        optionally substituted alkylthio or alkylsulphonyl, in each case        optionally substituted aryl or arylalkyl or optionally        substituted cycloalkyl.-   R² preferably represents fluorine, chlorine, bromine, iodine;    C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,    C₁-C₄-haloalkylthio, C₁-C₄-alkylsulphonyl, C₁-C₄-haloalkylsulphinyl,    C₁-C₄-haloalkylsulphonyl or cyano.-   R³ preferably represents fluorine, chlorine, bromine, iodine;    C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,    C₁-C₄-haloalkylthio, C₁-C₄-haloalkylsulphinyl,    C₁-C₄-haloalkylsulphonyl or cyano.-   R⁴ preferably represents hydrogen, cyanomethyl or    C₁-C₄-alkoxy-carbonyl.-   R¹ particularly preferably represents in each case optionally    substituted oxadiazolyl or thiadiazolyl, exemplary substituents    being: C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,    C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, and also phenyl or benzyl,    each of which is optionally mono- to trisubstituted by identical or    different substituents from the group consisting of halogen,    C₁-C₄-haloalkyl and C₁-C₄-haloalkoxy;    -   and also represents optionally substituted tetrazolyl, exemplary        substituents being: C₁-C₄-alkyl, C₁-C₄-haloalkyl,        C₁-C₄-alkylthio, C₁-C₄-alkylsulphonyl, furthermore phenyl or        benzyl, each of which is optionally mono- to trisubstituted by        identical or different substituents from the group consisting of        halogen, C₁-C₄-haloalkyl and C₁-C₄-haloalkoxy, furthermore        cyclopentyl or cyclohexyl, each of which is optionally mono- to        trisubstituted by identical or different substituents from the        group consisting of C₁-C₄-alkyl.-   R² particularly preferably represents fluorine, chlorine, bromine,    iodine, cyano; C₁-C₂-alkylthio, C₁-C₂-alkylsulphonyl and also    C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy; C₁-C₂-haloalkylthio or    C₁-C₂-haloalkylsulphonyl having in each case 1 to 5 identical or    different halogen atoms from the group consisting of fluorine,    chlorine and bromine.-   R³ particularly preferably represents chlorine, bromine, iodine,    cyano; and also represents C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy,    C₁-C₂-haloalkylthio, C₁-C₂-haloalkylsulphinyl or    C₁-C₂-haloalkylsulphonyl having in each case 1 to 5 identical or    different halogen atoms from the group consisting of fluorine,    chlorine and bromine.-   R⁴ particularly preferably represents hydrogen, cyanomethyl or    C₁-C₄-alkoxy-carbonyl.-   R¹ very particularly preferably represents the thiadiazolyls and    oxadiazolyls below:    -   where    -   X¹ and X² independently of one another represent hydrogen,        C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio,        C₁-C₄-haloalkylthio and also represent phenyl or benzyl, each of        which is optionally mono- to trisubstituted by identical or        different substituents from the group consisting of halogen,        C₁-C₂-haloalkyl and C₁-C₂-haloalkoxy having in each case 1 to 3        identical or different halogen atoms from the group consisting        of fluorine, chlorine and bromine;    -   and also represents the following tetrazolyls:    -   where    -   X³ and X⁴ independently of one another represent hydrogen,        C₁-C₄-alkyl, C₁-C₂-haloalkyl having 1 to 3 identical or        different halogen atoms from the group consisting of fluorine,        chlorine and bromine; C₁-C₄-alkylthio, C₁-C₄-alkylsulphonyl,        represent phenyl or benzyl, each of which is optionally mono- to        trisubstituted by identical or different substituents from the        group consisting of halogen, C₁-C₂-haloalkyl or C₁-C₂-haloalkoxy        having in each case 1 to 3 identical or different halogen atoms        from the group consisting of fluorine, chlorine and bromine, and        also represent cyclopentyl or cyclohexyl, each of which is        optionally mono- to trisubstituted by C₁-C₄-alkyl.-   R² very particularly preferably represents fluorine, chlorine,    bromine, iodine, methylthio, trifluoromethyl, trifluoromethoxy or    trifluoromethylthio.-   R³ very particularly preferably represents chlorine, bromine,    iodine, cyano; trifluoromethyl, trifluoromethoxy,    trifluoromethylthio, trifluoromethyl-sulphinyl or    trifluoromethylsulphonyl.-   R⁴ very particularly preferably represents hydrogen, cyanomethyl,    methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl or n-, i-,    s- or t-butoxycarbonyl.-   R¹ especially preferably represents the thiadiazolyls and    oxadiazolyls below:    -   where    -   X¹ and X² independently of one another represent hydrogen;        methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,        trifluoromethyl, trifluoromethoxy or trifluoromethylthio and        also represent phenyl or benzyl, each of which is optionally        mono- or disubstituted by identical or different substituents        from the group consisting of fluorine, chlorine, bromine,        trifluoromethyl and trifluoromethoxy;    -   and also represents the following tetrazolyls:    -   where    -   X³ and X⁴ independently of one another represent hydrogen;        methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl;        fluoromethyl, difluoromethyl, trifluoro-methyl,        1,1-difluoroethyl, 2,2,2-trifluoroethyl, methylthio, ethylthio,        methylsulphonyl, ethylsulphonyl; represent phenyl or benzyl,        each of which is optionally mono- or disubstituted by identical        or different substituents from the group consisting of fluorine,        chlorine, bromine, methyl, methoxy, trifluoromethyl and        trifluoromethoxy, and also represent cyclohexyl which is        optionally mono- or disubstituted by methyl.-   R² especially preferably represents fluorine, chlorine, bromine,    iodine, methylthio, trifluoromethyl, trifluoromethoxy or    trifluoromethylthio.-   R³ especially preferably represents chlorine, bromine, iodine,    cyano, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,    trifluoromethyl-sulphinyl or trifluoromethylsulphonyl.-   R⁴ especially preferably represents hydrogen or cyanomethyl.

Very particular preference is furthermore given to compounds of theformula (I) in which R¹ represents optionally substituted tetrazolyl,possible substituents being: C₁-C₄-alkyl, C₁-C₄-haloalkyl,C₁-C₄-alkylthio, C₁-C₄-alkylsulphonyl, furthermore phenyl or benzyl,each of which is optionally mono- to trisubstituted by identical ordifferent substituents from the group consisting of halogen,C₁-C₄-haloalkyl and C₁-C₄-haloalkoxy, furthermore cyclopentyl orcyclohexyl, each of which is optionally mono- to trisubstituted byidentical or different C₁-C₄-alkyl.

Very particular preference is furthermore given to compounds of theformula (I) in which R² represents chlorine.

Very particular preference is furthermore given to compounds of theformula (I) in which R⁴ represents hydrogen.

Very particular preference is furthermore given to compounds of theformula (I) in which R⁴ represents cyanomethyl.

Very particular preference is furthermore given to compounds of theformula (I) in which R³ represents trifluoromethoxy ortrifluoromethylthio.

The abovementioned general or preferred radical definitions orillustrations apply to the end products and, correspondingly, tostarting materials and intermediates. These radical definitions can becombined with one another as desired, i.e. including combinationsbetween the respective preferred ranges.

Preference according to the invention is given to compounds of theformula (I) which contain a combination of meanings listed above asbeing preferred (preferable).

Particular preference according to the invention is given to compoundsof the formula (I) which contain a combination of the meanings listedabove as being particularly preferred.

Very particular preference according to the invention is given tocompounds of the formula (I) which contain a combination of the meaningslisted above as being very particularly preferred.

Special preference according to the invention is given to compounds ofthe formula (I) which contain a combination of the meanings listed aboveas being especially preferred.

In the radical definitions given above and below, hydrocarbon radicals,such as alkyl, are in each case straight-chain or branched as far asthis is possible—including in combination with heteroatoms such asalkoxy.

Using, for example,3-(4-chlorophenyl)-4-(5-methyl-1,3,4-thiadiazol-2-yl)-4,5-dihydro-1H-pyrazoleand 4-trifluoromethoxyphenyl isocyanate as starting materials, thecourse of the process (a) according to the invention can be representedby the formula scheme below:

Using, for example,N-(4-trifluoromethoxy)-3-(4-chlorophenyl)-4-(5-methyl-1,3,4-thiadiazol-2-yl)-4,5-dihydro-1-pyrazolcarboxanilideand bromacetonitrile as starting materials, the course of the reactionof the process (b) according to the invention can be represented by thefollowing formula scheme:

Using, for example, N-cyanomethyl-4-trifluoromethoxyaniline, phosgeneand 3-(4-chlorophenyl)-4-(5-methyltetrazol-2-yl)-4,5-dihydro-1H-pyrazoleas starting materials, the course of the process (c) according to theinvention can be represented by the following formula scheme:

The formula (II) provides a general definition of the pyrazolines to beused as starting materials for carrying out the processes (a) and (c)according to the invention. In this formula, R¹ and R² preferably,particularly preferably, very particularly preferably and especiallypreferably have those meanings which have already been mentioned inconnection with the description of the compounds of the formula (I)according to the invention as being preferred, particularly preferred,very particularly preferred and especially preferred for these radicals.

The pyrazolines of the formula (II) are novel and also form part of thesubject-matter of this application. They are obtained by reactingsubstituted acetophenones of the formula (VII)

in which

-   R¹ and R² are as defined above-   in a first step with known bis-dialkylaminomethanes of the formula    (VII)    (Alk)₂N—CH₂—N(Alk)₂  (VIII)    in which-   Alk represents C₁-C₄-alkyl, preferably methyl,-   in the presence of an inert organic solvent (preferably a    halogenated hydrocarbon, such as, for example, methylene chloride or    ethylene chloride) at temperatures between 0° C. and 120° C.,    preferably between 20° C. and 80° C. (cf., for example, EP-A 0 546    420), and, if appropriate, isolating the resulting dialkylaminoalkyl    ketones of the formula (IX)    in which-   R¹, R² and Alk are as defined above-   and reacting these in a second step with hydrazine (hydrate) in the    presence of an inert organic solvent (preferably an alcohol, such    as, for example, methanol or ethanol) at temperatures between 0° C.    and 80° C., preferably between 20° C. and 50° C. (cf. also the    Preparation Examples).

Some of the substituted acetophenones of the formula (VII) are known(cf., for example, Chemiker-Zeitung 1989, 113, 217-219; Synthesis 1988,453-55; J. Chem. Soc., Perkin Trans. 1 1986, 1157-63; Chemiker-Zeitung1985, 109, 432-433 and WO 99/08678) and/or they can be obtained in agenerally known manner.

Thus, for example, the acetophenones of the formula (VIIa)

in which

-   R² and X⁴ are as defined above-   can be obtained by reacting haloacetophenones of the formula (X)    in which-   R² is as defined above and-   Hal² represents halogen, preferably chlorine or bromine,-   with tetrazoles of the formula (XI)    in which-   X⁴ is as defined above    in the presence of an organic or inorganic base (for example    potassium carbonate) and, if appropriate, in the presence of an    inert organic solvent (for example acetonitrile) at temperatures    between 0° C. and 100° C., preferably between 20° C. and 80° C. (cf.    also the Preparation Examples).

The haloacetophenones of the formula (X) and the tetrazoles of theformula (XI) are generally known compounds of organic chemistry and/orcan be obtained in a generally known manner.Acetophenones of the Formula (VII b)

in which

-   R² and X³ are as defined above-   can be obtained by reacting 2-cyanoacetophenones of the formula    (XII)    in which-   R² is as defined above-   with sodium azide and amine hydrochloride (for example triethylamine    hydrochloride) in the presence of an inert solvent (for example    acetonitrile, dimethylformamide, toluene), preferably under reflux    (cf. also the Preparation Examples) and, if appropriate, reacting    the resulting acetophenones of the formula (VII c)    in which-   R² is as defined above-   with compounds of the formula (XIII)    E-X³⁻¹  (XII)    in which-   X³⁻¹ represents C₁-C₄-alkyl, C₁-C₂-haloalkyl having 1 to 3 identical    or different halogen atoms from the group consisting of fluorine,    chlorine and bromine; C₁-C₄-alkylthio, C₁-C₄-alkylsulphonyl,    represents phenyl or benzyl, each of which is optionally mono- to    trisubstituted by identical or different substituents from the group    consisting of halogen, C₁-C₂-haloalkyl and C₁-C₂-haloalkoxy having    in each case 1 to 3 identical or different halogen atoms from the    group consisting of fluorine, chlorine and bromine, and also    represents cyclopentyl or cyclohexyl, each of which is optionally    mono- to trisubstituted by C₁-C₄-alkyl, and-   E represents an anionic leaving group, preferably chlorine, bromine,    iodine, acetoxy, tosyl or mesyl-   in the presence of an organic or inorganic base (for example    potassium carbonate) and, if appropriate, in the presence of an    inert organic solvent (for example acetonitrile) at temperatures    between 0° C. and 80° C., preferably between 10° C. and 50° C. (cf.    also the Preparation Examples).

When preparing acetophenones of the formula (VIIb) in which X³represents a tertiary alkyl radical, it is in some cases advantageous toreact the acetophenones of the formula (VIIc) with tertiary alcohols inthe presence of strong acids, such as, for example, trifluoroacetic acidand/or sulphuric acid.

The 2-cyanoacetophenones of the formula (XII) and the compounds of theformula (XIII) are generally known compounds of organic chemistry and/orcan be obtained in a generally known manner.The Acetophenones of the Formula (VII d)

in which

-   R² and X¹ are as defined above-   can be obtained by reacting ethyl benzoates of the formula (XIV)    in which-   R² is as defined above-   with methylthiadiazoles of the formula (XV)    in which-   X¹ is as defined above-   in the presence of a strong base (for example sodium hydride or    tert-butyllithium) in the presence of an inert organic solvent (for    example toluene), preferably under reflux (cf. also Chemiker-Zeitung    1989, 113, 217-219).

Acetophenones having other thiadiazolyl radicals can be obtained in acorresponding manner.

The ethyl benzoates of the formula (XIV) and the methylthiadiazoles ofthe formula (XV) are generally known compounds of organic chemistryand/or can be obtained in a generally known manner.

The Acetophenones of the formula (VII e)

in which

-   R² and X² are as defined above-   can be obtained by refluxing amidoximes of the formula (XVI)    in which-   R² is as defined above-   in a customary manner with appropriate X²-substituted acetic acid    derivatives, such as, preferably alkyl esters or anhydrides.

The amidoximes of the formula (XVI) can be obtained in a generally knownmanner by reacting 2-cyanoacetophenones of formula (XII) or ketalsthereof with hydroxylamine hydrochloride in the presence of a base (forexample potassium carbonate).

The acetophenones of the formula (VII f)

in which

-   R² and X² are as defined above-   can be obtained by refluxing hydrazides of the formula (XVII)    in which-   R² is as defined above-   in a customary manner with appropriate X²-substituted acetic acid    derivatives, such as, preferably, alkyl esters, also in the form of    corresponding ortho esters.

The hydrazides of the formula (XVII) can be obtained in a generallyknown manner by reacting corresponding ester derivatives with hydrazine.

The acetophenones of the formula (VII g)

in which

-   R² and X² are as defined above-   can be obtained by refluxing esters of the formula (XVIII)    in which-   R² and Alk are as defined above-   in a customary manner with amidoximes of the formula (XIX)    in which-   X² is as defined above.

The esters of the formula (XVIII) and the amidoximes of the formula(XIX) are generally known compounds of organic chemistry and/or can beobtained in a generally known manner.

The formula (III) provides a general definition of the isocyanatesfurther to be used as starting materials in the process (a) according tothe invention. In this formula, R³ preferably, particularly preferably,very particularly preferably and especially preferably has thosemeanings which have already been mentioned in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred, particularly preferred, very particularlypreferred and especially preferred for this radical.

The isocyanates of the formula (III) are generally known compounds oforganic chemistry and/or can be obtained in a generally known manner.

The formula (IV) provides a general definition of the halides to be usedas starting materials for carrying out the process (b) according to theinvention. In this formula, R⁴ preferably, particularly preferably, veryparticularly preferably and especially preferably has those meaningswhich have already been mentioned in connection with the description ofthe compounds of the formula (I) according to the invention as beingpreferred, particularly preferred, very particularly preferred andespecially preferred for this radical. Hal¹ preferably representschlorine or bromine.

The halides of the formula (IV) are generally known compounds of organicchemistry.

The formula (V) provides a general definition of the anilines to be usedas starting materials for carrying out the process (c) according to theinvention. In this formula, R³ and R⁴ preferably, particularlypreferably, very particularly preferably and especially preferably havethose meanings which have already been mentioned in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred, particularly preferred, very particularlypreferred and especially preferred for these radicals.

The anilines of the formula (V) are generally known compounds of organicchemistry and/or can be obtained in a generally known manner.

The process (a) according to the invention is preferably carried outusing diluents. Suitable diluents are virtually all inert organicsolvents. These preferably include aliphatic and aromatic, optionallyhalogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane,petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylenechloride, ethylene chloride, chloroform, carbon tetrachloride,chlorobenzene and o-dichlorobenzene, ethers, such as diethyl ether,dibutyl ether, methyl tert-butyl ether, methyl tert-amyl ether, glycoldimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane;ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketoneor methyl isobutyl ketone, esters, such as methyl acetate or ethylacetate, nitriles, such as, for example, acetonitrile or propionitrile,amides, such as, for example, dimethylformamide, dimethylacetamide andN-methylpyrrolidone, and also dimethyl sulphoxide, tetramethylenesulphone or hexamethyl phosphoric triamide.

The process (a) according to the invention is preferably also carriedout using a catalyst. Suitable catalysts are in particular tertiaryorganic amines, such as, for example, triethylamine.

The reaction temperatures in the process (a) according to the inventioncan be varied within a relatively wide range. In general, the process iscarried out at temperatures between 0° C. and 120° C., preferably attemperatures between 20° C. and 80° C.

The process (a) according to the invention is generally carried outunder atmospheric pressure. However, it is also possible to operateunder elevated or reduced pressure.

For carrying out the process (a) according to the invention, thestarting materials are generally employed in approximately equimolaramounts. However, it is also possible to use a relatively small excessof one of the two components employed. Work-up is carried out bycustomary methods (cf. the Preparation Examples).

The processes (b) and (c) according to the invention are preferablycarried out using diluents. Suitable diluents are virtually all inertorganic solvents. These preferably include aliphatic and aromatic,optionally halogenated hydrocarbons, such as pentane, hexane, heptane,cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene,xylene, methylene chloride, ethylene chloride, chloroform, carbontetrachloride, chlorobenzene and o-dichlorobenzene, ethers, such asdiethyl ether, dibutyl ether, glycol dimethyl ether and diglycoldimethyl ether, tetrahydrofuran and dioxane; ketones, such as acetone,methyl ethyl ketone, methyl isopropyl ketone or methyl isobutyl ketone,esters, such as methyl acetate or ethyl acetate, nitriles, such as, forexample, acetonitrile or propionitrile, amides, such as, for example,dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and alsodimethyl sulphoxide, tetramethylene sulphone or hexamethyl phosphorictriamide.

Suitable bases for carrying out the processes (b) and (c) according tothe invention are all acid binders which are customarily used for suchreactions. Preferred are alkali metal and alkaline earth metal hydrides,such as lithium hydride, sodium hydride, potassium hydride or calciumhydride; alkali metal and alkaline earth metal hydroxides, such aslithium hydroxide, sodium hydroxide, potassium hydroxide or calciumhydroxide; alkali metal and alkaline earth metal carbonates orbicarbonates, such as sodium carbonate, sodium bicarbonate, potassiumcarbonate, potassium bicarbonate or calcium carbonate; alkali metalacetates, such as sodium acetate or potassium acetate, alkali metalalcohols, such as sodium tert-butoxide or potassium tert-butoxide;further basic nitrogen compounds, such as trimethylamine, triethylamine,tripropylamine, tributylamine, diisobutylamine, dicyclohexylamine,ethyldiisopropylamine, ethyldicyclohexylamine, N,N-dimethylbenzylamine,N,N-dimethylaniline, pyridine, 2-methyl-, 3-methyl-, 4-methyl-,2,4-dimethyl-, 2,6-dimethyl-, 2-ethyl-, 4-ethyl- and5-ethyl-2-methylpyridine, 1,5-diazabicyclo[4.3.0]non-5-ene (DBN),1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,4-diazabicyclo[2.2.2]-octane(DABCO).

The reaction temperatures in the process (b) according to the inventioncan be varied within a relatively wide range. In general, the process iscarried out at temperatures between 0° C. and 120° C., preferably attemperatures between 20° C. and 80° C.

The process (b) according to the invention is generally carried outunder atmospheric pressure. However, it is also possible to operateunder elevated or reduced pressure.

For carrying out the process (b) according to the invention, thestarting materials are generally employed in approximately equimolaramounts. However, it is also possible to employ an excess of halide andbase. Work-up is carried out by customary methods (cf. the PreparationExamples).

The reaction temperatures in the process (c) according to the inventioncan be varied within a relatively wide range. In general, the process iscarried out at temperatures between −10° C. and 120° C., preferably attemperatures between 0° C. and 100° C.

The process (c) according to the invention is generally carried outunder atmospheric pressure. However, it is also possible to operateunder elevated or reduced pressure.

For carrying out the process (c) according to the invention, thestarting materials are generally employed in approximately equimolaramounts. However, it is also possible to employ an excess of chlorideand base. Work-up is carried out by customary methods (cf. thePreparation Examples).

The active compounds, according to the invention, having good planttolerance and favourable warm-blood toxicity, are suitable forcontrolling animal pests, in particular insects, arachnids andnematodes, which are encountered in agriculture, in forestry, in theprotection of stored products and of materials, and in the hygienesector. They may be preferably used as crop protection agents. They areactive against normally sensitive and resistant species and against allor some stages of development. The abovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spp.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Acheta domesticus,Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp. andSchistocerca gregaria.

From the order of the Blattaria, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae and Blattella germanica.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Phthiraptera, for example, Pediculus humanuscorporis, Haematopinus spp., Linognathus spp., Trichodectes spp. andDamalinia spp.

From the order of the Thysanoptera, for example, Hercinothripsfemoralis, Thrips tabaci, Thrips palmi and Frankliniella accidentalis.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosomalanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp.,Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi,Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecaniumcomi, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens,Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psyllaspp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella xylostella, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Mamestra brassicae, Panolisflammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pierisspp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleriamellonella, Tineola bisselliella, Tinea pellionella, Hofinannophilapseudospretella, Cacoecia podana, Capua reticulana, Choristoneurafumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana,Cnaphalocerus spp. and Oulema oryzae.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis, Costelytra zealandica and Lissorhoptrusoryzophilus.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae,Tipula paludosa, Hylemyia spp. and Liriomyza spp.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp.

From the class of the Arachnida, for example, Scorpio maurus,Latrodectus mactans, Acarus siro, Argas spp., Omithodoros spp.,Derrnanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora,Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp.,Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemusspp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.,Hemitarsonemus spp. and Brevipalpus spp.

The plant-parasitic nematodes include, for example, Pratylenchus spp.,Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans,Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp.,Longidorus spp., Xiphinema spp., Trichodorus spp. and Bursaphelenchusspp.

The compounds according to the invention can be used with particularlygood results for controlling plant-damaging insects, such as, forexample, against caterpillars of the cotton bud worm (Heliothisvirescens and Heliothis armigera), the larvae of the mustard beetle(Phaedon cochliariae), the eggs and/or larvae and caterpillars of thediamondback moth (Plutella xylostella) and the caterpillars of the armyworm (Spodoptera exigua and Spodoptera frugioerda).

At certain concentrations or application rates, the compounds accordingto the invention may, if appropriate, also be used as herbicides andmicrobicides, for example as fungicides, antimycotics and bactericides.If appropriate, they may also be used as intermediates or precursors forthe synthesis of further active compounds.

All plants and plant parts can be treated in accordance with theinvention. Plants are to be understood as meaning in the present contextall plants and plant populations such as desired and undesired wildplants or crop plants (inclusive of naturally occurring crop plants).Crop plants can be plants which can be obtained by conventional plantbreeding and optimization methods or by biotechnological and recombinantmethods or by combinations of these methods, inclusive of the transgenicplants and inclusive of the plant cultivars protectable or notprotectable by plant breeders' rights. Plant parts are to be understoodto mean all above-ground and underground parts and organs of plants,such as shoot, leaf, flower and root, examples which may be mentionedbeing leaves, needles, stalks, stems, flowers, fruit bodies, fruits,seeds, roots, tubers and rhizomes. The plant parts also includeharvested material, and vegetative and generative propagation material,for example cuttings, tubers, rhizomes, offsets and seeds.

Treatment according to the invention of the plants and plant parts withthe active compounds is carried out directly or by allowing thecompounds to act on their surroundings, environment or storage space bythe customary treatment methods, for example by immersion, spraying,evaporation, fogging, scattering, painting on and, in the case ofpropagation material, in particular in the case of seeds, also byapplying one or more coats.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusts, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and microencapsulations in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surfactants, that isemulsifiers and/or dispersants, and/or foam-formers.

If the extender used is water, it is also possible to employ for exampleorganic solvents as auxiliary solvents. Essentially, suitable liquidsolvents are: aromatics such as xylene, toluene or alkylnaphthalenes,chlorinated aromatics or chlorinated aliphatic hydrocarbons such aschlorobenzenes, chloroethylenes or methylene chloride, aliphatichydrocarbons such as cyclohexane or paraffins, for example petroleumfractions, mineral and vegetable oils, alcohols such as butanol orglycol and also their ethers and esters, ketones such as acetone, methylethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polarsolvents such as dimethylformamide and dimethyl sulphoxide, and alsowater.

Suitable solid carriers are:

-   for example ammonium salts and ground natural minerals such as    kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or    diatomaceous earth, and ground synthetic minerals, such as finely    divided silica, alumina and silicates; suitable solid carriers for    granules are: for example crushed and fractionated natural rocks    such as calcite, marble, pumice, sepiolite and dolomite, and also    synthetic granules of inorganic and organic meals, and granules of    organic material such as sawdust, coconut shells, maize cobs and    tobacco stalks; suitable emulsifiers and/or foam-formers are: for    example nonionic and anionic emulsifiers, such as polyoxyethylene    fatty acid esters, polyoxyethylene fatty alcohol ethers, for example    alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates,    arylsulphonates and also protein hydrolysates; suitable dispersants    are: for example lignosulphite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyes, such asalizarin dyes, azo dyes and metal phthalocyanine dyes, and tracenutrients such as salts of iron, manganese, boron, copper, cobalt,molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be employed as suchor in their formulations as a mixture with known fungicides,bactericides, acaricides, nematicides or insecticides, for example inorder to increase the activity spectrum or avoid the development ofresistance. In many cases synergistic effects are achieved, ie. theefficacy of the mixture is greater than the efficacy of the individualcomponents.

Suitable examples of co-components in mixtures are the followingcompounds:

Fungicides:

-   aldimorph, ampropylfos, ampropylfos-potassium, andoprim, anilazine,    azaconazole, azoxystrobin,-   benalaxyl, benodanil, benomyl, benzamacril, benzamacril-isobutyl,    bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S,    bromuconazole, bupirimate, buthiobate,-   calcium polysulphide, carpropamid, capsimycin, captafol, captan,    carbendazim, carboxin, carvon, quinomethionate, chlobenthiazone,    chlorfenazole, chloroneb, chloropicrin, chlorothalonil,    chlozolinate, clozylacon, cufraneb, cymoxanil, cyproconazole,    cyprodinil, cyprofuram,-   debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine,    dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph,    diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione,    ditalimfos, dithianon, dodemorph, dodine, drazoxolon,-   edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,-   famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram,    fenhexamide, fenitropan, fenpiclonil, fenpropidin, fenpropimorph,    fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam,    flumetover, fluoromide, fluquinconazole, flurprimidol, flusilazole,    flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium,    fosetyl-sodium, fthalide, fuberidazole, furalaxyl, furametpyr,    furcarbonil, furconazole, furconazole-cis, furmecyclox,-   guazatine,-   hexachlorobenzene, hexaconazole, hymexazole,-   imazalil, imibenconazole, iminoctadine, iminoctadine albesilate,    iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP),    iprodione, iprovalicarb, irumamycin, isoprothiolane, isovaledione,-   kasugamycin, kresoxim-methyl, copper preparations, such as: copper    hydroxide, copper naphthenate, copper oxychloride, copper sulphate,    copper oxide, oxine-copper and Bordeaux mixture,-   mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil,    metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram,    metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,-   nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,-   ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim,    oxyfenthiin,-   paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen,    picoxystrobin, pimaricin, piperalin, polyoxin, polyoxorim,    probenazole, prochloraz, procymidone, propamocarb,    propanosine-sodium, propiconazole, propineb, pyraclostrobin,    pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,-   quinconazole, quintozene (PCNB), quinoxyfen-   sulphur and sulphur preparations, spiroxamine,-   tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole,    thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram,    tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol,    triazbutil, triazoxide, trichlamide, tricyclazole, tridemorph,    trifloxystrodin, triflumizole, triforine, triticonazole,-   uniconazole,-   validamycin A, vinclozolin, viniconazole,-   zarilamide, zineb, ziram and also-   Dagger G,-   OK-8705, OK-8801,-   α-(1,1-dimethylethyl)-β-(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol,-   α-(2,4-dichlorophenyl)-β-fluoro-β-propyl-1H-1,2,4-triazole-1-ethanol,-   α-(2,4-dichlorophenyl)-β-methoxy-α-methyl-1H-1,2,4-triazole-1-ethanol,-   α-(5-methyl-1,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-1H-1,2,4-triazole-1-ethanol,-   (5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone,-   (E)-α-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,-   1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-ethanone-O-(phenylmethyl)-oxime,-   1-(2-methyl-1-naphthalenyl)-1H-pyrrole-2,5-dione,-   1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,-   1-[(diiodomethyl)-sulphonyl]-4-methyl-benzene,-   1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole,-   1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole,-   1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole,-   1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinol,-   2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide,-   2,6-dichloro-5-(methylthio)-4-pyrimidinyl-thiocyanate,-   2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,-   2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,-   2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,-   2-[(1-methylethyl)-sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole,-   2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-α-D-glucopyranosyl]-amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,-   2-aminobutane,-   2-bromo-2-(bromomethyl)-pentanedinitrile,-   2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide,-   2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,-   2-phenylphenol (OPP),-   3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrole-2,5-dione,-   3,5-dichloro-N-[cyano-[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide,-   3-(1,1-dimethylpropyl)-1-oxo-1H-indene-2-carbonitrile,-   3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,-   4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulphonamide,-   4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one,-   8-hydroxyquinoline sulphate,-   9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic hydrazide,-   bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophenedicarboxylate,-   cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,-   cis-4-[3-[4-(1,1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethylmorpholinehydrochloride,-   ethyl [(4-chlorophenyl)-azo]-cyanoacetate,-   potassium hydrogen carbonate,-   methanetetrathiol sodium salt,-   methyl    1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,-   methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,-   methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,-   N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,-   N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,-   N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulphonamide,-   N-(4-cyclohexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,-   N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,-   N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide,-   N-(6-methoxy)-3-pyridinyl)-cyclopropanecarboxamide,-   N-[2,2,2-trichloro-1-[(chloroacetyl)-amino]-ethyl]-benzamide,-   N-[3-chloro-4,5-bis-(2-propinyloxy)-phenyl]-N′-methoxy-methanimidamide,-   N-formyl-N-hydroxy-DL-alanine sodium salt,-   O,O-diethyl    [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate,-   O-methyl S-phenyl phenylpropylphosphoramidothioate,-   S-methyl 1,2,3-benzothiadiazole-7-carbothioate,-   spiro[2H]-1-benzopyrane-2,1′(3′H)-isobenzofuran-3′-one-   4-[(3,4-dimethoxyphenyl)-3-(4-fluorophenyl)acryloyl]morpholine.    Bactericides:-   bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,    kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,    probenazole, streptomycin, tecloftalam, copper sulphate and other    copper preparations.    Insecticides/Acaricides/Nematicides:-   abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb,    aldoxycarb, alphacypermethrin, alphamethrin, amitraz, avermectin, AZ    60541, azadirachtin, azamethiphos, azinphos A, azinphos M,    azocyclotin,-   Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus    thuringiensis, Baculoviruses, Beauveria bassiana, Beauveria tenella,    bendiocarb, benfuracarb, bensultap, benzoximate, betacyfluthrin,    bifenazate, bifenthrin, bioethanomethrin, biopermethrin,    bistrifluron, BPMC, bromophos A, bufencarb, buprofezin, butathiofos,    butocarboxim, butylpyridaben,-   cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan,    cartap, chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos,    chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,    chlovaporthrin, chromafenozide, cis-resmethrin, cispermethrin,    clocythrin, cloethocarb, clofentezine, clothianidine, cyanophos,    cycloprene, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin,    cypermethrin, cyromazine,-   deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron,    diazinon, dichlorvos, dicofol, diflubenzuron, dimethoate,    dimethylvinphos, diofenolan, disulfoton, docusat-sodium, dofenapyn,-   eflusilanate, emamectin, empenthrin, endosulfan, Entomopfthora spp.,    esfenvalerate, ethiofencarb, ethion, ethoprophos, etofenprox,    etoxazole, etrimfos,-   fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion,    fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad,    fenpyrithrin, fenpyroximate, fenvalerate, fipronil, fluazuron,    flubrocythrinate, flucycloxuron, flucythrinate, flufenoxuron,    flumethrin, flutenzine, fluvalinate, fonophos, fosmethilan,    fosthiazate, fubfenprox, furathiocarb,-   granulosis viruses,-   halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox,    hydroprene,-   imidacloprid, indoxacarb, isazofos, isofenphos, isoxathion,    ivermectin,-   nuclear polyhedrosis viruses,-   lambda-cyhalothrin, lufenuron,-   malathion, mecarbam, metaldehyde, methamidophos, metharhizium    anisopliae, metharhizium flavoviride, methidathion, methiocarb,    methoprene, methomyl, methoxyfenozide, metolcarb, metoxadiazone,    mevinphos, milbemectin, milbemycin, monocrotophos,-   naled, nitenpyram, nithiazine, novaluron,-   omethoate, oxamyl, oxydemethon M,-   Paecilomyces fumosoroseus, parathion A, parathion M, permethrin,    phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim,    pirimicarb, pirimiphos A, pirimiphos M, profenofos, promecarb,    propargite, propoxur, prothiofos, prothoate, pymetrozine,    pyraclofos, pyresmethrin, pyrethrum, pyridaben, pyridathion,    pyrimidifen, pyriproxyfen,-   quinalphos,-   ribavirin,-   salithion, sebufos, silafluofen, spinosad, spirodiclofen, sulfotep,    sulprofos,-   tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos,    teflubenzuron, tefluthrin, temephos, temivinphos, terbufos,    tetrachlorvinphos, tetradifon, thetacypermethrin, thiacloprid,    thiamethoxam, thiapronil, thiatriphos, thiocyclam hydrogen oxalate,    thiodicarb, thiofanox, thuringiensin, tralocythrin, tralomethrin,    triarathene, triazamate, triazophos, triazurone, trichlophenidine,    trichlorfon, triflumuron, trimethacarb,-   vamidothion, vaniliprole, Verticillium lecanii,-   YI 5302,-   zeta-cypermethrin, zolaprofos,-   (1R-cis)-[5-(phenylmethyl)-3-furanyl]-methyl    3-[(dihydro-2-oxo-3(2H)-furanylidene)-methyl]-2,2-dimethylcyclopropanecarboxylate,-   (3-phenoxyphenyl)-methyl 2,2,3,3-tetramethylcyclopropanecarboxylate,-   1-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2(1H)-imine,-   2-(2-chloro-6-fluorophenyl)-4-[4-(1,1-dimethylethyl)phenyl]-4,5-dihydro-oxazole,-   2-(acetyloxy)-3-dodecyl-1,4-naphthalenedione,-   2-chloro-N-[[[4-(1-phenylethoxy)-phenyl]-amino]-carbonyl]-benzamide,-   2-chloro-N-[[[4-(2,2-dichloro-1,1-difluoroethoxy)-phenyl]-amino]-carbonyl]-benzamide,-   3-methylphenyl propylcarbamate,-   4-[4-(4-ethoxyphenyl)-4-methylpentyl]-1-fluoro-2-phenoxy-benzene,-   4-chloro-2-(1,1-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-3(2H)-pyridazinone,-   4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-pyridazinone,-   4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorophenyl)-3(2H)-pyridazinone,-   Bacillus thuringiensis strain EG-2348,-   [2-benzoyl-1-(1,1-dimethylethyl)-hydrazinobenzoic acid,-   2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]dec-3-en-4-yl    butanoate,-   [3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]-cyanamide,-   dihydro-2-(nitromethylene)-2H-1,3-thiazine-3(4H)-carboxaldehyde,-   ethyl    [2-[[1,6-dihydro-6-oxo-1-(phenylmethyl)-4-pyridazinyl]oxy]ethyl]-carbamate,-   N-(3,4,4-trifluoro-1-oxo-3-butenyl)-glycine,-   N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide,-   N-[(2-chloro-5-thiazolyl)methyl]-N′-methyl-N″-nitro-guanidine,-   N-methyl-N′-(1-methyl-2-propenyl)-1,2-hydrazinedicarbothioamide,-   N-methyl-N′-2-propenyl-1,2-hydrazinedicarbothioamide,-   O,O-diethyl    [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate,-   N-cyanomethyl-4-trifluoromethylnicotinamide,-   3,5-dichloro-1-(3,3-dichloro-2-propenyloxy)-4-[3-(5-trifluoromethylpyridin-2-yloxy)propoxy]benzene.

A mixture with other known active compounds, such as herbicides, or withfertilizers and growth regulators is also possible.

The active compounds according to the invention can furthermore bepresent when used as insecticides in their commercially availableformulations and in the use forms, prepared from these formulations, asa mixture with synergistic agents. Synergistic agents are compoundswhich increase the action of the active compounds, without it beingnecessary for the synergistic agent added to be active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and pests of stored products, the activecompound is distinguished by an excellent residual action on wood andclay as well as a good stability to alkali on limed substrates.

As already mentioned above, it is possible to treat all plants and theirparts according to the invention. In a preferred embodiment, wild plantspecies and plant cultivars, or those obtained by conventionalbiological breeding, such as crossing or protoplast fusion, and partsthereof, are treated. In a further preferred embodiment, transgenicplants and plant cultivars obtained by genetic engineering, ifappropriate in combination with conventional methods (Genetic ModifiedOrganisms), and parts thereof are treated. The term “parts” or “parts ofplants” or “plant parts” has been explained above.

Particularly preferably, plants of the plant cultivars which are in eachcase commercially available or in use are treated according to theinvention. Plant cultivars are to be understood as meaning plants havingcertain properties (“traits”) which have been obtained by conventionalbreeding, by mutagenesis or by recombinant DNA techniques. These can bevarieties, bio- and genotypes.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the substances and compositions to be used according to theinvention, better plant growth, increased tolerance to high or lowtemperatures, increased tolerance to drought or to water or soil saltcontent, increased flowering performance, easier harvesting, acceleratedmaturation, higher harvest yields, better quality and/or a highernutritional value of the harvested products, better storage stabilityand/or processability of the harvested products are possible whichexceed the effects which were actually to be expected.

The transgenic plants or plant cultivars (i.e. those obtained by geneticengineering) which are preferably treated according to the inventioninclude all plants which, in the genetic modification, received geneticmaterial which imparted particularly advantageous useful traits to theseplants. Examples of such traits are better plant growth, increasedtolerance to high or low temperatures, increased tolerance to drought orto water or soil salt content, increased flowering performance, easierharvesting, accelerated maturation, higher harvest yields, betterquality and/or a higher nutritional value of the harvested products,better storage stability and/or processability of the harvestedproducts. Further and particularly emphasized examples of such traitsare a better defence of the plants against animal and microbial pests,such as against insects, mites, phytopathogenic fungi, bacteria and/orviruses, and also increased tolerance of the plants to certainherbicidally active compounds. Examples of transgenic plants which maybe mentioned are the important crop plants, such as cereals (wheat,rice), maize, soya beans, potatoes, cotton, oilseed rape and also fruitplants (with the fruits apples, pears, citrus fruits and grapevines),and particular emphasis is given to maize, soya beans, potatoes, cottonand oilseed rape. Traits that are emphasized are in particular increaseddefence of the plants against insects by toxins formed in the plants, inparticular those formed by the genetic material from Bacillusthuringiensis (for example by the genes CryIA(a), CryIA(b), CryIA(c),CryIIA, CryIIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF and alsocombinations thereof) (hereinbelow referred to as “Bt plants”). Traitsthat are also particularly emphasized are the increased defence of theplants to fungi, bacteria and viruses by systemic acquired resistance(SAR), systemin, phytoalexins, elicitors and resistance genes andcorrespondingly expressed proteins and toxins. Traits that arefurthermore particularly emphasized are the increased tolerance of theplants to certain herbicidally active compounds, for exampleimidazolinones, sulphonylureas, glyphosate or phosphinotricin (forexample the “PAT” gene). The genes which impart the desired traits inquestion can also be present in combination with one another in thetransgenic plants. Examples of “Bt plants” which may be mentioned aremaize varieties, cotton varieties, soya bean varieties and potatovarieties which are sold under the trade names YIELD GARD® (for examplemaize, cotton, soya beans), KnockOut® (for example maize), StarLink®(for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf(potato). Examples of herbicide-tolerant plants which may be mentionedare maize varieties, cotton varieties and soya bean varieties which aresold under the trade names Roundup Ready® (tolerance to glyphosate, forexample maize, cotton, soya bean), Liberty Link® (tolerance tophosphinotricin, for example oilseed rape), IMI® (tolerance toimidazolinones) and STS® (tolerance to sulphonylureas, for examplemaize). Herbicide-resistant plants (plants bred in a conventional mannerfor herbicide tolerance) which may be mentioned include the varietiessold under the name Clearfield® (for example maize). Of course, thesestatements also apply to plant cultivars having these orstill-to-be-developed genetic traits, which plants will be developedand/or marketed in the future.

The plants listed can be treated according to the invention in aparticularly advantageous manner with the compounds of the generalformula (I) or the active compound mixtures according to the invention.The preferred ranges stated above for the active compounds or mixturesalso apply to the treatment of these plants. Particular emphasis isgiven to the treatment of plants with the compounds or the mixturesspecifically mentioned in the present text.

The active compounds according to the invention act not only againstplant, hygiene and stored product pests, but also in the veterinarymedicine sector against animal parasites (ectoparasites), such as hardticks, soft ticks, mange mites, leaf mites, flies (biting and licking),parasitic fly larvae, lice, hair lice, feather lice and fleas. Theseparasites include:

From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.

From the order of the Mallophagida and the suborders Amblycerina andIschnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp. and Felicola spp.

From the order Diptera and the suborders Nematocerina and Brachycerina,for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp.,Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp.,Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopotaspp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp.,Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossinaspp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp.,Hippobosca spp., Lipoptena spp. and Melophagus spp.

From the order of the Siphonapterida, for example, Pulex spp.,Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.

From the order of the Heteropterida, for example, Cimex spp., Triatomaspp., Rhodnius spp. and Panstrongylus spp.

From the order of the Blattarida, for example, Blatta orientalis,Periplaneta americana, Blattela germanica and Supella spp.

From the subclass of the Acaria (Acarida) and the orders of the Meta-and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobiusspp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp.,Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp.,Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Omithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

The active compounds of the formula (I) according to the invention arealso suitable for controlling arthropods which infest agriculturalproductive livestock, such as, for example, cattle, sheep, goats,horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys,ducks, geese and bees, other pets, such as, for example, dogs, cats,caged birds and aquarium fish, and also so-called test animals, such as,for example, hamsters, guinea pigs, rats and mice. By controlling thesearthropods, cases of death and reduction in productivity (for meat,milk, wool, hides, eggs, honey etc.) should be diminished, so that moreeconomic and easier animal husbandry is possible by use of the activecompounds according to the invention.

The active compounds according to the invention are used in theveterinary sector in a known manner by enteral administration in theform of, for example, tablets, capsules, potions, drenches, granules,pastes, boluses, the feed-through process and suppositories, byparenteral administration, such as, for example, by injections(intramuscular, subcutaneous, intravenous, intraperitoneal and thelike), implants, by nasal administration, by dermal use in the form, forexample, of dipping or bathing, spraying, pouring on and spotting on,washing and powdering, and also with the aid of moulded articlescontaining the active compound, such as collars, ear marks, tail marks,limb bands, halters, marking devices and the like.

When used for cattle, poultry, pets and the like, the active compoundsof the formula (I) can be used as formulations (for example powders,emulsions, free-flowing compositions), which comprise the activecompounds in an amount of 1 to 80% by weight, directly or after 100 to10 000-fold dilution, or they can be used as a chemical bath.

It has furthermore been found that the compounds according to theinvention also have a strong insecticidal action against insects whichdestroy industrial materials.

The following insects may be mentioned as examples and as beingpreferred—but without any limitation:

Beetles, such as

-   Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum,    Xestobium rufovillosum, Ptilinus pecticomis, Dendrobium pertinex,    Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus    africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens,    Trogoxylon aequale, Minthes rugicollis, Xyleborus spec.,    Tryptodendron spec., Apate monachus, Bostrychus capucins,    Heterobostrychus brunneus, Sinoxylon spec. and Dinoderus minutus.

Hymenopterons, such as

-   Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerus    augur.

Termites, such as

-   Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,    Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes    lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis and    Coptotermes formosanus.

Bristletails, such as Lepisma saccharina.

Industrial materials in the present context are to be understood asmeaning non-living materials, such as, preferably, plastics, adhesives,sizes, papers and cards, leather, wood and processed wood products andcoating compositions.

Wood and processed wood products are materials to be protected,especially preferably, from insect infestation.

Wood and processed wood products which can be protected by the agentaccording to the invention or mixtures comprising this are to beunderstood as meaning, for example:

-   building timber, wooden beams, railway sleepers, bridge components,    boat jetties, wooden vehicles, boxes, pallets, containers, telegraph    poles, wood panelling, wooden windows and doors, plywood, chipboard,    joinery or wooden products which are used quite generally in    house-building or in building joinery.

The active compounds according to the invention can be used as such, inthe form of concentrates or in generally customary formulations, such aspowders, granules, solutions, suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active compounds according to the invention withat least one solvent or diluent, emulsifier, dispersing agent and/orbinder or fixing agent, a water repellent, if appropriate siccatives andUV stabilizers and if appropriate dyes and pigments, and also otherprocessing auxiliaries.

The insecticidal compositions or concentrates used for the preservationof wood and wood-derived timber products comprise the active compoundaccording to the invention in a concentration of 0.0001 to 95% byweight, in particular 0.001 to 60% by weight.

The amount of the compositions or concentrates employed depends on thenature and occurrence of the insects and on the medium. The optimumamount employed can be determined for the use in each case by a seriesof tests. In general, however, it is sufficient to employ 0.0001 to 20%by weight, preferably 0.001 to 10% by weight, of the active compound,based on the material to be preserved.

Solvents and/or diluents which are used are an organic chemical solventor solvent mixture and/or an oily or oil-like organic chemical solventor solvent mixture of low volatility and/or a polar organic chemicalsolvent or solvent mixture and/or water, and if appropriate anemulsifier and/or wetting agent.

Organic chemical solvents which are preferably used are oily or oil-likesolvents having an evaporation number above 35 and a flashpoint above30° C., preferably above 45° C. Substances which are used as such oilyor oil-like water-insoluble solvents of low volatility are appropriatemineral oils or aromatic fractions thereof, or solvent mixturescontaining mineral oils, preferably white spirit, petroleum and/oralkylbenzene.

Mineral oils having a boiling range from 170 to 220° C., white spirithaving a boiling range from 170 to 220° C., spindle oil having a boilingrange from 250 to 350° C., petroleum and aromatics having a boilingrange from 160 to 280° C., turpentine oil and the like, areadvantageously employed.

In a preferred embodiment, liquid aliphatic hydrocarbons having aboiling range from 180 to 210° C. or high-boiling mixtures of aromaticand aliphatic hydrocarbons having a boiling range from 180 to 220° C.and/or spindle oil and/or monochloronaphthalene, preferablyα-monochloronaphthalene, are used.

The organic oily or oil-like solvents of low volatility which have anevaporation number above 35 and a flashpoint above 30° C., preferablyabove 45° C., can be replaced in part by organic chemical solvents ofhigh or medium volatility, providing that the solvent mixture likewisehas an evaporation number above 35 and a flashpoint above 30° C.,preferably above 45° C., and that the insecticide/fungicide mixture issoluble or emulsifiable in this solvent mixture.

According to a preferred embodiment, some of the organic chemicalsolvent or solvent mixture is replaced by an aliphatic polar organicchemical solvent or solvent mixture. Aliphatic organic chemical solventscontaining hydroxyl and/or ester and/or ether groups, such as, forexample, glycol ethers, esters or the like, are preferably used.

Organic chemical binders which are used in the context of the presentinvention are the synthetic resins and/or binding drying oils which areknown per se, are water-dilutable and/or are soluble or dispersible oremulsifiable in the organic chemical solvents employed, in particularbinders consisting of or comprising an acrylate resin, a vinyl resin,for example polyvinyl acetate, polyester resin, polycondensation orpolyaddition resin, polyurethane resin, alkyd resin or modified alkydresin, phenolic resin, hydrocarbon resin, such as indene-cumarone resin,silicone resin, drying vegetable oils and/or drying oils and/orphysically drying binders based on a natural and/or synthetic resin.

The synthetic resin used as the binder can be employed in the form of anemulsion, dispersion or solution. Bitumen or bituminous substances canalso be used as binders in an amount of up to 10% by weight. Dyestuffs,pigments, water-repelling agents, odour correctants and inhibitors oranticorrosive agents and the like which are known per se canadditionally be employed.

It is preferred according to the invention for the composition orconcentrate to comprise, as the organic chemical binder, at least onealkyd resin or modified alkyd resin and/or one drying vegetable oil.Alkyd resins having an oil content of more than 45% by weight,preferably 50 to 68% by weight, are preferably used according to theinvention.

All or some of the binder mentioned can be replaced by a fixing agent(mixture) or a plasticizer (mixture). These additives are intended toprevent evaporation of the active compounds and crystallization orprecipitation. They preferably replace 0.01 to 30% of the binder (basedon 100% of the binder employed).

The plasticizers originate from the chemical classes of phthalic acidesters, such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoricacid esters, such as tributyl phosphate, adipic acid esters, such asdi-(2-ethylhexyl) adipate, stearates, such as butyl stearate or amylstearate, oleates, such as butyl oleate, glycerol ethers or highermolecular weight glycol ethers, glycerol esters and p-toluenesulphonicacid esters.

Fixing agents are based chemically on polyvinyl alkyl ethers, such as,for example, polyvinyl methyl ether or ketones, such as benzophenone orethylenebenzophenone.

Possible solvents or diluents are, in particular, also water, ifappropriate as a mixture with one or more of the abovementioned organicchemical solvents or diluents, emulsifiers and dispersing agents.

Particularly effective preservation of wood is achieved by impregnationprocesses on a large industrial scale, for example vacuum, double vacuumor pressure processes.

The ready-to-use compositions can also comprise other insecticides, ifappropriate, and also one or more fungicides, if appropriate.

Possible additional mixing partners are, preferably, the insecticidesand fungicides mentioned in WO 94/29 268. The compounds mentioned inthis document are an explicit constituent of the present application.

Especially preferred mixing partners which may be mentioned areinsecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin,cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25,flufenoxuron, hexaflumuron, transfluthrin, thiacloprid, methoxyphenoxideand triflumuron,

-   and also fungicides, such as epoxyconazole, hexaconazole,    azaconazole, propiconazole, tebuconazole, cyproconazole,    metconazole, imazalil, dichlorfluanid, tolylfluanid,    3-iodo-2-propinyl-butyl carbamate, N-octyl-isothiazolin-3-one and    4,5-dichloro-N-octylisothiazolin-3-one.

The compounds according to the invention can at the same time beemployed for protecting objects which come into contact with salt wateror brackish water, such as hulls, screens, nets, buildings, moorings andsignalling systems, against fouling.

Fouling by sessile Oligochaeta, such as Serpulidae, and by shells andspecies from the Ledamorpha group (goose barnacles), such as variousLepas and Scalpellum species, or by species from the Balanomorpha group(acorn barnacles), such as Balanus or Pollicipes species, increases thefrictional drag of ships and, as a consequence, leads to a markedincrease in operation costs owing to higher energy consumption andadditionally frequent residence in dry dock.

Apart from fouling by algae, for example Ectocarpus sp. and Ceramiumsp., fouling by sessile Entomostraka groups, which come under thegeneric term Cirripedia (cirriped crustaceans), is of particularimportance.

Surprisingly, it has now been found that the compounds according to theinvention, alone or in combination with other active compounds, have anoutstanding antifouling action.

Using the compounds according to the invention, alone or in combinationwith other active compounds, allows the use of heavy metals such as, forexample, in bis-(trialkyltin) sulphides, tri-n-butyltin laurate,tri-n-butyltin chloride, copper(I) oxide, triethyltin chloride,tri-n-butyl-(2-phenyl-4-chlorophenoxy)tin, tributyltin oxide, molybdenumdisulphide, antimony oxide, polymeric butyl titanate,phenyl-(bispyridine)-bismuth chloride, tri-n-butyltin fluoride,manganese ethylenebisthiocarbamate, zinc dimethyldithiocarbamate, zincethylenebisthiocarbamate, zinc salts and copper salts of 2-pyridinethiol1-oxide, bisdimethyldithiocarbamoylzinc ethylene-bisthiocarbamate, zincoxide, copper(I)ethylene-bisdithiocarbamate, copper thiocyanate, coppernaphthenate and tributyltin halides to be dispensed with, or theconcentration of these compounds to be substantially reduced.

If appropriate, the ready-to-use antifouling paints can additionallycomprise other active compounds, preferably algicides, fungicides,herbicides, molluscicides, or other antifouling active compounds.

Preferably suitable components in combinations with the antifoulingcompositions according to the invention are:

-   algicides such as-   2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine,    dichlorophen, diuron, endothal, fentin acetate, isoproturon,    methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;-   fungicides such as-   benzo[b]thiophenecarboxylic acid cyclohexylamide S,S-dioxide,    dichlofluanid, fluorfolpet, 3-iodo-2-propinyl butylcarbamate,    tolylfluanid and azoles such as azaconazole, cyproconazole,    epoxyconazole, hexaconazole, metconazole, propiconazole and    tebuconazole;-   molluscicides such as-   fentin acetate, metaldehyde, methiocarb, niclosamid, thiodicarb and    trimethacarb;-   or conventional antifouling active compounds such as    4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatryl    sulphone, 2-(N,N-dimethylthiocarbamoylthio)-5-nitrothiazyl,    potassium, copper, sodium and zinc salts of 2-pyridinethiol 1-oxide,    pyridine-triphenylborane, tetrabutyldistannoxane,    2,3,5,6-tetrachloro-4-(methylsulphonyl)-pyridine,    2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram disulphide    and 2,4,6-trichlorophenylmaleimide.

The antifouling compositions used comprise the active compound accordingto the invention of the compounds according to the invention in aconcentration of 0.001 to 50% by weight, in particular 0.01 to 20% byweight.

Moreover, the antifouling compositions according to the inventioncomprise the customary components such as, for example, those describedin Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, AntifoulingMarine Coatings, Noyes, Park Ridge, 1973.

Besides the algicidal, fungicidal, molluscicidal active compounds andinsecticidal active compounds according to the invention, antifoulingpaints comprise, in particular, binders.

Examples of recognized binders are polyvinyl chloride in a solventsystem, chlorinated rubber in a solvent system, acrylic resins in asolvent system, in particular in an aqueous system, vinyl chloride/vinylacetate copolymer systems in the form of aqueous dispersions or in theform of organic solvent systems, butadiene/styrene/acrylonitrilerubbers, drying oils such as linseed oil, resin esters or modifiedhardened resins in combination with tar or bitumens, asphalt and epoxycompounds, small amounts of chlorine rubber, chlorinated polypropyleneand vinyl resins.

If appropriate, paints also comprise inorganic pigments, organicpigments or colorants which are preferably insoluble in salt water.Paints may furthermore comprise materials such as colophonium to allowcontrolled release of the active compounds. Furthermore, the paints maycomprise plasticizers, modifiers which affect the rheological propertiesand other conventional constituents. The compounds according to theinvention or the abovementioned mixtures may also be incorporated intoself-polishing antifouling systems.

The active compounds are also suitable for controlling animal pests, inparticular insects, arachnids and mites, which are found in enclosedspaces such as, for example, dwellings, factory halls, offices, vehiclecabins and the like. They can be employed in domestic insecticideproducts for controlling these pests alone or in combination with otheractive compounds and auxiliaries. They are active against sensitive andresistant species and against all development stages. These pestsinclude:

From the order of the Scorpionidea, for example, Buthus occitanus.

From the order of the Acarina, for example, Argas persicus, Argasreflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus,Omithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi,Neutrombicula autumnalis, Dermatophagoides pteronissimus andDermatophagoides forinae.

From the order of the Araneae, for example, Aviculariidae and Araneidae.

From the order of the Opiliones, for example, Pseudoscorpiones chelifer,Pseudoscorpiones cheiridium and Opiliones phalangium.

From the order of the Isopoda, for example, Oniscus asellus andPorcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus andPolydesmus spp.

From the order of the Chilopoda, for example, Geophilus spp.

From the order of the Zygentoma, for example, Ctenolepisma spp., Lepismasaccharina and Lepismodes inquilinus.

From the order of the Blattaria, for example, Blatta orientalies,Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchloraspp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana,Periplaneta brunnea, Periplaneta fuliginosa and Supella longipalpa.

From the order of the Saltatoria, for example, Acheta domesticus.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Kalotermes spp. andReticulitermes spp.

From the order of the Psocoptera, for example, Lepinatus spp. andLiposcelis spp.

From the order of the Coleptera, for example, Anthrenus spp., Attagenusspp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp.,Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae,Sitophilus zeamais and Stegobium paniceum.

From the order of the Diptera, for example, Aedes aegypti, Aedesalbopictus, Aedes taeniorhynchus, Anopheles spp., Calliphoraerythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culexpipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Muscadomestica, Phlebotomus spp., Sarcophaga camaria, Simulium spp., Stomoxyscalcitrans and Tipula paludosa.

From the order of the Lepidoptera, for example, Achroia grisella,Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tineapellionella and Tineola bisselliella.

From the order of the Siphonaptera, for example, Ctenocephalides canis,Ctenocephalides felis, Pulex irritans, Tunga penetrans and Xenopsyllacheopis.

From the order of the Hymenoptera, for example, Camponotus herculeanus,Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis,Paravespula spp. and Tetramorium caespitum.

From the order of the Anoplura, for example, Pediculus humanus capitis,Pediculus humanus corporis and Phthirus pubis.

From the order of the Heteroptera, for example, Cimex hemipterus, Cimexlectularius, Rhodinus prolixus and Triatoma infestans.

They are used in the household insecticides sector alone or incombination with other suitable active compounds such as phosphoricesters, carbamates, pyrethroids, growth regulators or active compoundsfrom other known classes of insecticides.

They are used in aerosols, pressure-free spray products, for examplepump and atomizer sprays, automatic fogging systems, foggers, foams,gels, evaporator products with evaporator tablets made of cellulose orpolymer, liquid evaporators, gel and membrane evaporators,propeller-driven evaporators, energy-free, or passive, evaporationsystems, moth papers, moth bags and moth gels, as granules or dusts, inbaits for spreading or in bait stations.

PREPARATION EXAMPLES Example 1

(Process a)

At 70° C., 1 g (5 mmol) of 4-trifluoromethylphenyl isocyanate is addedto a mixture of 1.3 g (5 mmol) of3-(4-chlorophenyl)-4-(5-methyltetrazol-2-yl)-4,5-dihydro-1H-pyrazole,0.1 ml of triethylamine and 50 ml of methyl tert-butyl ether. Themixture is stirred at 70° C. for 15 minutes and then allowed to slowlycool to room temperature. The solvent is then distilled off underreduced pressure and residue is purified by silica gel chromatography(methylene chloride/diethyl ether 5:1).

This gives 1.2 g (52% of theory) ofN-(4-trifluoromethoxy)-3-(4-chlorophenyl)-4-(5-methyltetrazol-2-yl)-4,5-dihydro-1-pyrazolecarboxanilideof logP (pH 2.3) 4.00.Preparation of the Starting Material

At room temperature, 2.16 g (0.021 mol) of bisdimethylaminomethane areadded to a solution of 5 g (0.02 mol) of2-(5-methyltetrazol-2-yl)-4′-chloroacetophenone in 50 ml of methylenechloride, and the mixture is boiled at reflux for 18 hours. The solventis then distilled off under reduced pressure and residue is dissolved in50 ml of ethanol. 1.13 g (0.0226 mol) of hydrazine hydrate are added,and the reaction mixture is then stirred at 30° C. for 3 hours. Theprecipitated product is filtered off with suction and washed with alittle cold ethanol and with water.

This gives 3.3 g (61% of theory) of3-(4-chlorophenyl)-4-(5-methyltetrazol-2-yl)-4,5-dihydro-1H-pyrazole oflogP (pH 2.3)=2.11.Preparation of the Precursor

A mixture of 17.5 g (0.075 mol) of 2-bromo-4′-chloroacetophenone, 6.3 g(0.075 mol) of 5-methyltetrazole, 12.4 g (0.09 mol) of potassiumcarbonate and 200 ml of acetonitrile is stirred at room temperature for16 hours. The solvent is then distilled off under reduced pressure,about 200 ml of water are added to the residue and the mixture isextracted with ethyl acetate. The organic phase is dried over sodiumsulphate and concentrated under reduced pressure.

This gives 17.5 g of a mixture of the two isomers2-(5-methyltetrazol-2-yl)-4′-chloroacetophenone of logP (pH 2.3)=2.14and 2-(5-methyltetrazol-1-yl)-4′-chloroacetophenone of logP (pH2.3)=1.81. The target product is removed by silica gel chromatography(methylene chloride/ethyl acetate 10:1). This gives 6.3 g (35% oftheory) of colourless crystals.

Example 2

(Process c)

At 0° C., 1.5 g (5.6 mmol) ofN-cyanomethyl-N-(4-trifluoromethoxy)phenyl-carbamoyl chloride are addeddropwise to a solution of 1.3 g (5 mmol) of3-(4-chlorophenyl)-4-(5-methyltetrazol-2-yl)-4,5-dihydro-1H-pyrazole and0.84 ml (6 mmol) of triethylamine in 30 ml of methylene chloride, andthe mixture is boiled under reflux for 3.5 hours. The mixture is thenstirred at room temperature for 18 hours and then washed twice with ineach case 100 ml of water. The organic phase is dried over sodiumsulphate and concentrated under reduced pressure. The residue ispurified by silica gel chromatography (methylene chloride/diethyl ether7:1).

This gives 1.7 g (68% of theory) ofN-cyanomethyl-N-trifluoromethoxy-3-(4-chlorophenyl)-4-(5-methyltetrazol-2-yl)-4,5-dihydro-1-pyrazolecarboxanilideof logP (pH 2.3)=3.68.Preparation of the Starting Material

At 0° C., a solution of 20.7 g (0.0958 mol) ofN-cyanomethyl-4-trifluoromethoxyaniline and 11.6 g (0.115 mol) oftriethylamine in 150 ml of toluene is added to a solution of 10.4 g(0.105 mol) of phosgene in 100 ml of toluene, and the mixture is stirredat room temperature for 18 hours. Excess phosgene is then aspirated. Thereaction mixture is washed twice with cold water, the organic phase isdried with sodium sulphate and the solvent is then distilled off underreduced pressure.

This gives 26.3 g (94% of theory) ofN-cyanomethyl-N-(4-trifluoromethoxy)-phenylcarbamoyl chloride ofrefractive index n_(D) ²⁰=1.4816.

Example 3

(Process a)

At 70° C., 0.7 g (3 mmol) of 4-trifluoromethylphenyl isocyanate is addedto a mixture of 0.8 g (3 mmol) of3-(4-chlorophenyl)-4-(2-methyltetrazol-5-yl)-4,5-dihydro-1H-pyrazole,0.1 ml of triethylamine and 50 ml of methyl tert-amyl ether. The mixtureis stirred at 70° C. for 15 minutes and then allowed to slowly cool toroom temperature. The precipitated product is filtered off with suction.

This gives 1.2 g (52% of theory) ofN-(4-trifluoromethoxy)-3-(4-chlorophenyl)-4-(5-methyltetrazol-2-yl)-4,5-dihydro-1-pyrazolecarboxanilideof logP (pH 2.3)=4.25.Preparation of the Starting Material

At room temperature, 1.6 g (0.016 mol) of bisdimethylaminomethane areadded to a solution of 3.5 g (0.015 mol) of2-(2-methyltetrazol-5-yl)-4′-chloroacetophenone in 50 ml of methylenechloride, and the mixture is boiled under reflux for 18 hours. Thesolvent is then distilled off under reduced pressure and the residue isdissolved in 50 ml of ethanol. 0.85 g (0.017 mol) of hydrazine hydrateis added, and the reaction mixture is then stirred at 30° C. for 3hours. The solvent is then distilled off under reduced pressure at abath temperature of at most 30° C., the residue is triturated with alittle ethanol and the product is filtered off after crystallization andwashed with ethanol and with water.

This gives 1.7 g (44% of theory) of3-(4-chlorophenyl)-4-(2-methyltetrazol-5-yl)-4,5-dihydro-1H-pyrazole oflogP (pH 2.3)=1.67.Preparation of the Precursor

A mixture of 13 g (0.058 mol) of 2-tetrazol-5-yl-4′-chloroacetophenone,9.7 g (0.07 mol) of potassium carbonate, 10 g (0.07 mol) of methyliodide and 100 ml of acetonitrile is stirred at room temperature for 16hours. The solvent is then distilled off under reduced pressure, about200 ml of water are added to the residue and the mixture is extractedwith ethyl acetate. The organic phase is dried over sodium sulphate andconcentrated under reduced pressure.

This gives 12.2 g of a mixture of the two isomers2-(2-methyltetrazol-5-yl)-4′-chloroacetophenone of logP (pH 2.3)=2.03and 2-(1-methyltetrazol-5-yl)-4′-chloroacetophenone of logP (pH2.3)=1.78. The target product is separated off by silica gelchromatography (methylene chloride/diethyl ether 3:1). This gives 3.5 g(21% of theory) of colourless crystals.

A mixture of 15 g (0.084 mol) of 2-cyano-4′-chloroacetophenone, 14.4 g(0.105 mol) of triethylamine hydrochloride, 6.9 g (0.105 mol) of sodiumazide and 100 ml of toluene is boiled under reflux for 72 hours. Thesolvent is then distilled off under reduced pressure, the residue isdissolved in 200 ml of about 5% strength aqueous sodium hydroxidesolution and insoluble particles are filtered off. Using dilutehydrochloric acid, the filtrate is adjusted to about pH 2 and theprecipitated product is then filtered off with suction and washed withwater. The crude product is dissolved in excess sodium bicarbonatesolution, the solution is filtered and the filtrate is once moreadjusted to about pH 2 using dilute hydrochloric acid. The precipitatedproduct is filtered off and washed with water.

This gives 16.2 g (87% of theory) of2-tetrazol-5-yl-4′-chloroacetophenone of logP (pH 2.3)=1.44.

Example 4

(Process a)

At 70° C., 1 g (5 mmol) of 4-trifluoromethoxyphenyl isocyanate is addedto a mixture of 1.4 g (5 mmol) of3-(4-chlorophenyl)-4-(5-methyl-1,3,4-thiadiazol-2-yl)-4,5-dihydro-1H-pyrazole,0.1 ml of triethylamine and 50 ml of methyl tert-amyl ether. The mixtureis stirred at 70° C. for 15 minutes and then allowed to slowly cool toroom temperature. The solvent is then distilled off under reducedpressure and the residue is purified by silica gel chromatography(methylene chloride/diethyl ether 7:1).

This gives 0.15 g (6% of theory) ofN-(4-trifluoromethoxy)-3-(4-chlorophenyl)-4-(5-methyl-1,3,4-thiadiazol-2-yl)-4,5-dihydro-1-pyrazolecarboxanilideof logP (pH 2.3)=3.77.Preparation of the Starting Material

At room temperature, 1.9 g (0.0187 mol) of bisdimethylaminomethane isadded to a solution of 4.5 g (0.018 mol) of2-(2-methyl-1,3,4-thiadiazol-5-yl)-4′-chloroacetophenone (preparationsee Chemiker-Zeitung 1989, 113, 217-219) in 50 ml of methylene chloride,and the mixture is boiled under reflux for 18 hours. The solvent is thendistilled off under reduced pressure and the residue is dissolved in 50ml of ethanol. 1 g (0.02 mol) of hydrazine hydrate is added, and thereaction mixture is then stirred at 30° C. for 3 hours. The solvent isthen distilled off under reduced pressure at a bath temperature of atmost 30° C., about 200 ml of water are added to the residue and themixture is extracted with ethyl acetate. The organic phase is dried oversodium sulphate and concentrated under reduced pressure.

This gives 4.9 g (98% of theory) of3-(4-chlorophenyl)-4-(2-methyl-1,3,4-thiadiazol-5-yl)-4,5-dihydro-1H-pyrazoleof logP (pH 2.3)=1.77.

The compounds of the formula (I) listed in Table 1 below can be obtainedanalogously to Examples 1 to 4 and/or in accordance with the generalstatements on the preparation: TABLE 1 (I)

Ex. R¹ R² R³ R⁴ logP (pH2.3) 5

Cl OCF₃ H 2.47 6

Br OCF₃ H 4.84 7

Br SCF₃ H 5.22 8

Cl OCF₃ H 3.86 9

Cl SCF₃ CH₂CN 3.94 10

Cl SCF₃ H 4.36 11

Cl SCF₃ H 4.16 12

Cl OCF₃ CH₂CN 3.42 13

Cl SCF₃ CH₂CN 3.68 14

Cl OCF₃ H 15

Cl SCF₃ H

The compounds of the formula (II) listed in Table 2 below can beobtained analogously to Examples 1, 3 and 4 and/or in accordance withthe general statements on the preparation: TABLE 2 (II)

Ex.No. R¹ R² logP (pH2.3) II-4

Cl 1.63 II-5

Br 2.74 II-6

Cl 1.54

The compounds of the formula (VII) listed in Table 3 below can beobtained analogously to Examples 1 and 3 and/or in accordance with thegeneral statements on the preparation: TABLE 3 (VII)

Ex.No. R¹ R² logP (pH2.3) VII-4

Cl 1.78 VII-5

Cl 1.79 VII-6

Br 3.19 VII-7

Cl 1.78

The logP values given in the tables and Preparation Examples above aredetermined in accordance with EEC directive 79/831 Annex V.A8 by HPLC(High Performance Liquid Chromatography) using a reversed-phase column(C 18). Temperature: 43° C.

The determination is carried out in the acidic range at pH 2.3 using themobile phases 0.1% aqueous phosphoric acid and acetonitrile; lineargradient from 10% acetonitrile to 90% acetonitrile.

Calibration is carried out using unbranched alkan-2-ones (of 3 to 16carbon atoms) with known logP values (determination of the logP valuesby retention times using linear interpolation between two successivealkanones).

The lambda max values were determined in the maxima of thechromatographic signals using the UV spectra from 200 nm to 400 nm.

USE EXAMPLES Example A

Heliothis armigera Test

-   Solvent: 7 parts by weight of dimethylformamide-   Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Soya bean shoots (Glycine max) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with caterpillars of the cotton bud worm (Heliothis armigera)while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars have been killed.

In this test, at an exemplary active compound concentration of 500 ppm,the compounds 2, 4 and 10 of the Preparation Examples, for example, showa kill of 100% after 7 days.

Example B

Heliothis virescens Test

-   Solvent: 7 parts by weight of dimethylformamide-   Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Soya bean shoots (Glycine max) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with Heliothis virescens caterpillars while the leaves arestill moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars have been killed.

In this test, at an exemplary active compound concentration of 500 ppm,the compound 1 of the Preparation Examples, for example, shows a kill of100% after 7 days.

Example C

Phaedon larvae Test

-   Solvent: 7 parts by weight of dimethylformamide-   Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with larvae of the mustard beetle (Phaedon cochleariae) whilethe leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all beetle larvae have been killed; 0% means that none of thebeetle larvae have been killed.

In this test, at an exemplary active compound concentration of 500 ppm,the compounds 1, 2, 3, 4, 5, 8, 10 and 11 of the Preparation Examples,for example, show a kill of 100% after 7 days.

Example D

Plutella Test

-   Solvent: 7 parts by weight of dimethylformamide-   Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with caterpillars of the diamondback moth (Plutellaxylostella) while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars have been killed.

In this test, at an exemplary active compound concentration of 500 ppm,the compounds 1, 2, 4, and 10 of the Preparation Examples, for example,show a kill of 100% after 7 days.

Example E

Spodoptera exigua Test

-   Solvent: 7 parts by weight of dimethylformamide-   Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with caterpillars of the army worm (Spodoptera exigua) whilethe leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars have been killed.

In this test, at an exemplary active compound concentration of 500 ppm,the compounds 1, 2, 4, and 10 of the Preparation Examples, for example,show a kill of 100% after 7 days.

Example F

Spodoptera frugiperda Test

-   Solvent: 7 parts by weight of dimethylformamide-   Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with caterpillars of the army worm (Spodoptera frugiperda)while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars have been killed.

In this test, at an exemplary active compound concentration of 500 ppm,the compounds 1, 2, 3, 4, 5, 8, 10 and 11 of the Preparation Examples,for example, show a kill of 100% after 7 days.

Example G

Plutella Test

Solvent:

-   -   100 parts by weight of acetone    -   1900 parts by weight of methanol

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, and theconcentrate is diluted with methanol to the desired concentration.

A stated amount of active compound preparation of the desiredconcentration is pipetted onto a standardized amount of synthetic feed.After the methanol has evaporated, about 200-300 eggs of the diamondbackmoth (Plutella xylostella) are placed onto the feed.

After the desired period of time, the kill of the eggs and larvae isdetermined in %. 100% means that all animals have been killed; 0% meansthat none of the animals have been killed.

In this test, at an exemplary active compound concentration of 1000 ppm,compound 6 of the Preparation Examples, for example, shows a kill of100% and compound 7 of the Preparation Examples a kill of 95%, in eachcase after 7 days.

Example H

Diabrotica balteata Test (Larvae in Soil)

Critical concentration test/soil insects—treatment of transgenic plants

-   Solvent: 3 parts by weight of dimethylformamide-   Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

The preparation of active compound is mixed intimately with the soil.The concentration of the active compound in the preparation is virtuallyimmaterial, only the amount by weight of active compound per volume unitof soil, which is stated in ppm (mg/l) matters. The soil is filled into0.25 1 pots, and these are left to stand at 20° C.

Immediately after the preparation, 5 pregerminated maize corns of thecultivar YIELD GUARD (trade mark of Monsanto Comp., USA) are placed intoeach pot. After 2 days, the corresponding test insects are placed intothe treated soil. After a further 7 days, the efficacy of the activecompound is determined by counting the number of maize plants that haveemerged (1 plant=20% activity).

Example I

Heliothis virescens Test (Treatment of Transgenic Plants)

-   Solvent: 7 parts by weight of dimethylformamide-   Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Soya bean shoots (Glycine max) of the cultivar Roundup Ready (trade markof Monsanto Comp. USA) are treated by being dipped into the preparationof active compound of the desired concentration and are populated withthe tobacco budworm caterpillar Heliothis virescens while the leaves arestill moist.

After the desired period of time, the kill of the insects is determined.100% means that all caterpillars have been killed, 0% means that none ofthe caterpillars have been killed.

1-16. (canceled)
 17. A substituted 4-hetarylpyrazoline of formula (I)

in which R¹ represents optionally substituted oxadiazolyl, thiadiazolyl,or tetrazolyl, R² represents halogen, haloalkyl, alkoxy, haloalkoxy,alkylthio, haloalkylthio, alkylsulphonyl, haloalkylsulphinyl,haloalkylsulphonyl, or cyano, R³ represents halogen, haloalkyl, alkoxy,haloalkoxy, alkylthio, haloalkylthio, haloalkylsulphinyl,haloalkylsulphonyl, or cyano, and R⁴ represents hydrogen, cyanomethyl,or alkoxycarbonyl.
 18. A substituted 4-hetarylpyrazoline of formula (I)according to claim 17 in which R¹ represents optionally substitutedoxadiazolyl or thiadiazolyl, wherein the substituents are optionallysubstituted alkyl, optionally substituted alkoxy, optionally substitutedalkylthio, optionally substituted aryl, or optionally substitutedarylalkyl; or represents optionally substituted tetrazolyl, wherein thesubstituents are optionally substituted alkyl, optionally substitutedalkylthio or alkylsulphonyl, optionally substituted aryl or arylalkyl,or optionally substituted cycloalkyl, R² represents fluorine, chlorine,bromine, iodine, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, C₁-C₄-alkylsulphonyl,C₁-C₄-haloalkylsulphinyl, C₁-C₄-haloalkylsulphonyl, or cyano, R³represents fluorine, chlorine, bromine, iodine, C₁-C₄-haloalkyl,C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio,C₁-C₄-haloalkylsulphinyl, C₁-C₄-haloalkylsulphonyl, or cyano, and R⁴represents hydrogen, cyanomethyl, or C₁-C₄-alkoxy-carbonyl.
 19. Asubstituted 4-hetarylpyrazoline of formula (I) according to claim 17 inwhich R¹ represents optionally substituted oxadiazolyl or thiadiazolyl,wherein the substituents are C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, or C₁-C₄-haloalkylthio or are phenylor benzyl, each of which is optionally mono- to trisubstituted byidentical or different substituents selected from the group consistingof halogen, C₁-C₄-haloalkyl, and C₁-C₄-haloalkoxy; or representsoptionally substituted tetrazolyl, wherein the substituents areC₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio, or C₁-C₄-alkylsulphonyl,are phenyl or benzyl, each of which is optionally mono- totrisubstituted by identical or different substituents selected from thegroup consisting of halogen, C₁-C₄-haloalkyl, and C₁-C₄-haloalkoxy, orare cyclopentyl or cyclohexyl, each of which is optionally mono- totrisubstituted by identical or different substituents selected from thegroup consisting of C₁-C₄-alkyl, R² represents fluorine, chlorine,bromine, iodine, cyano, C₁-C₂-alkylthio, or C₁-C₂-alkylsulphonyl; orrepresents C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy; C₁-C₂-haloalkylthio, orC₁-C₂-haloalkylsulphonyl having in each case 1 to 5 identical ordifferent halogen atoms selected from the group consisting of fluorine,chlorine, and bromine, R³ represents chlorine, bromine, iodine, orcyano; or represents C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy,C₁-C₂-haloalkylthio, C₁-C₂-haloalkylsulphinyl, orC₁-C₂-haloalkylsulphonyl having in each case 1 to 5 identical ordifferent halogen atoms selected from the group consisting of fluorine,chlorine, and bromine, and R⁴ represents hydrogen, cyanomethyl, orC₁-C₄-alkoxy-carbonyl.
 20. A substituted 4-hetarylpyrazoline of formula(I) according to claim 17 in which R¹ represents the thiadiazolyls oroxadiazolyls

where X¹ and X² independently of one another represent hydrogen,C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio, or C₁-C₄-haloalkylthio;or represent phenyl or benzyl, each of which is optionally mono- totrisubstituted by identical or different substituents selected from thegroup consisting of halogen, C₁-C₂-haloalkyl, and C₁-C₂-haloalkoxyhaving in each case 1 to 3 identical or different halogen atoms selectedfrom the group consisting of fluorine, chlorine, and bromine; orrepresents the tetrazolyls

where X³ and X⁴ independently of one another represent hydrogen;C₁-C₄-alkyl; C₁-C₂-haloalkyl having 1 to 3 identical or differenthalogen atoms selected from the group consisting of fluorine, chlorine,and bromine; C₁-C₄-alkylthio; C₁-C₄-alkylsulphonyl; phenyl or benzyl,each of which is optionally mono- to trisubstituted by identical ordifferent substituents selected from the group consisting of halogen,C₁-C₂-haloalkyl, or C₁-C₂-haloalkoxy having in each case 1 to 3identical or different halogen atoms selected from the group consistingof fluorine, chlorine, and bromine; or cyclopentyl or cyclohexyl, eachof which is optionally mono- to trisubstituted by C₁-C₄-alkyl, R²represents fluorine, chlorine, bromine, iodine, methylthio,trifluoromethyl, trifluoromethoxy, or trifluoromethylthio, R³ representschlorine, bromine, iodine, cyano; trifluoromethyl, trifluoromethoxy,trifluoromethylthio, trifluoromethylsulphinyl, ortrifluoromethylsulphonyl, and R⁴ represents hydrogen, cyanomethyl,methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, or n-, i-, s-,or t-butoxycarbonyl.
 21. A substituted 4-hetarylpyrazoline of formula(I) according to claim 17 in which R¹ represents the thiadiazolyls oroxadiazolyls

where X¹ and X² independently of one another represent hydrogen; methyl,ethyl, n- or i-propyl, n-, i-, s-, or t-butyl, trifluoromethyl,trifluoromethoxy, or trifluoromethylthio; or represent phenyl or benzyl,each of which is optionally mono- or disubstituted by identical ordifferent substituents selected from the group consisting of fluorine,chlorine, bromine, trifluoromethyl, and trifluoromethoxy; or representsthe tetrazolyls

where X³ and X⁴ independently of one another represent hydrogen, methyl,ethyl, n- or i-propyl, n-, i-, s-, or t-butyl; fluoromethyl,difluoromethyl, trifluoromethyl, 1,1-difluoroethyl,2,2,2-trifluoroethyl, methylthio, ethylthio, methylsulphonyl, orethylsulphonyl; represent phenyl or benzyl, each of which is optionallymono- or disubstituted by identical or different substituents selectedfrom the group consisting of fluorine, chlorine, bromine, methyl,methoxy, trifluoromethyl, and trifluoromethoxy; or represent cyclohexylthat is optionally mono- or disubstituted by methyl, R² representsfluorine, chlorine, bromine, iodine, methylthio, trifluoromethyl,trifluoromethoxy, or trifluoromethylthio, R³ represents chlorine,bromine, iodine, cyano, trifluoromethyl, trifluoromethoxy,trifluoromethylthio, trifluoromethylsulphinyl, ortrifluoromethylsulphonyl, and R⁴ represents hydrogen or cyanomethyl. 22.A substituted 4-hetarylpyrazoline of formula (I) according to claim 17in which R¹ represents optionally substituted tetrazolyl, wherein thesubstituents are C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio, orC₁-C₄-alkylsulphonyl, are phenyl or benzyl, each of which is optionallymono- to trisubstituted by identical or different substituents selectedfrom the group consisting of halogen, C₁-C₄-haloalkyl, andC₁-C₄-haloalkoxy, or are cyclopentyl or cyclohexyl, each of which isoptionally mono- to trisubstituted by identical or differentC₁-C₄-alkyl.
 23. A substituted 4-hetarylpyrazoline of formula (I)according to claim 17 in which R² represents chlorine.
 24. A substituted4-hetarylpyrazoline of formula (I) according to claim 17 in which R⁴represents hydrogen.
 25. A substituted 4-hetarylpyrazoline of formula(I) according to claim 17 in which R⁴ represents cyanomethyl.
 26. Asubstituted 4-hetarylpyrazoline of formula (I) according to claim 17 inwhich R³ represents trifluoromethoxy or trifluoromethylthio.
 27. Aprocess for preparing a substituted 4-hetarylpyrazoline of formula (I)according to claim 17 comprising (a) reacting a pyrazoline of formula(II)

in which R¹ and R² are as defined for formula (I) in claim 17, with anisocyanate of formula (III)

in which R³ is as defined for formula (I) in claim 17, optionally in thepresence of a diluent and optionally in the presence of a catalyst,thereby forming a pyrazoline derivative of formula (Ia) according to theinvention

in which R¹, R² and R³ are as defined for formula (I) in claim 17; and(b) optionally reacting the pyrazoline derivative of formula (Ia) with ahalide of the formula (IV)Hal¹-R⁴  (IV) in which R⁴ is as defined for formula (I) in claim 17, andHal¹ represents halogen, optionally in the presence of a diluent andoptionally in the presence of a base; or (c) initially reacting ananiline of formula (V)

in which R³ and R⁴ are as defined for formula (I) in claim 17, withphosgene in the presence of a diluent and, optionally, in the presenceof a base, to form a carbamoyl chloride of formula (VI)

in which R³ and R⁴ are as defined for formula (I) in claim 17, andreacting the resultant carbamoyl chloride of formula (VI), directly orafter isolation, with a pyrazoline of formula (II)

in which R¹ and R² are as defined for formula (I) in claim 17, in thepresence of a diluent and, optionally, in the presence of a base.
 28. Apesticide comprising one or more compounds of formula (I) according toclaim 17 and one or more extenders and/or surfactants.
 29. A method forcontrolling pests comprising allowing an effective amount of one or morecompounds of formula (I) according to claim 17 act on pests and/or theirhabitat.
 30. A process for preparing pesticides comprising mixing one ormore compounds of formula (I) according to claim 17 with one or moreextenders and/or surfactants.